Static Hyperpolarizability Values Research Articles

Computational Design, Spectral, NBO, DOS, Bioactivity Evaluation, ADMET Analysis, Third-Order non-linear Optical and Quantum Chemical Investigations on Hydrogen Bonded Novel Organic Molecular Complex of 4-[Bis[2-(acetyloxy)ethyl]amino]benzaldehyde (4B2AEAB) Derivatives for Opto-Electronic Applications

In this paper, the authors reported a theoretical investigation on molecular structure, geometry optimization, global and local chemical reactivity descriptors calculations, NBO study, DOS, non-linear optical behaviour and vibrational wavenumbers of the novel 4-[bis[2- (acetyloxy)ethyl]amino]benzaldehyde (4B2AEAB) were carried out by DFT (B3LYP and B3PW91) methods with 6-31+G (d, p) basis set in water solvent. The calculated vibrational wavenumbers are found to be in good agreement with experimental FT-IR spectra and PED analysis using GaussView 5.0 and VEDA 4 program. The UV-Vis absorption spectrum of 4B2AEAB was calculated by using TD-DFT/B3LYP/6-31+G(d,p) in gas phase, water, CHCl3, DMSO and CH2Cl2 solvents using CPCM model and λmax in range of 354.16, 341.35, 343.74, 342.18 and 342.64 nm, respectively. The density of state (DOS spectrum) of the compound in term of HOMOs and LUMOs and MESP were calculated and analyzed. The temperature effects on the thermodynamic properties are also discussed. The calculated 1H NMR and 13C NMR chemical shift using GIAO method and solvent effect are investigated by B3LYP/6-31+G(d,p) in gas phase, chloroform, water, DMSO and CH2Cl2 solvents and correlate with experimental chemical shifts. The dipole moment, polarizability and the first static hyperpolarizability values show that the 4B2AEAB molecule is active non-linear optical (NLO) material. The nucleophilic and electrophilic reactive sites in the 4B2AEAB and its derivatives were analyzed by Fukui function analysis using Mulliken charge. The charge transfer, conjugative interactions and delocalization of electron density are analyzed by natural bond orbital (NBO) analysis. The biological properties and ADMET study of 4B2AEAB and its derivatives are also discussed.

Spectroscopic (FTIR, FT-Raman, 1H NMR and UV–Vis) and DFT/TD-DFT studies on cholesteno [4,6-b,c]-2′,5′-dihydro-1′,5′-benzothiazepine

The density functional theory calculations and spectroscopic characterization (FTIR, FT-Raman, 1H NMR and ultraviolet–visible) of the pharmaceutically active compound Cholesteno [4,6-b,c]-2′,5′-dihydro-1′,5′-benzothiazepine (CHBT) have been carried out. The recorded Vibrational, proton NMR and electronic spectra have been compared with the simulated one and they are found in well agreement. The bands appearing in FTIR and FT-Raman spectra are assigned with great accuracy using animated modes. The ultraviolet–visible (UV–Vis) absorption bands are assigned using molecular orbitals data obtained by TD-B3LYP/PCM calculations with 6-311G(d,p) basis set. Proton NMR signal peaks have been assigned using GIAO-B3LYP/6-311G(d,p)/PCM method. The hyperconjugative interactions and charge delocalization within the molecule have been studied using natural bond orbital (NBO) analysis. The non-linear optical (NLO) behavior of the present compound has been investigated using theoretical dipole moment, polarizability and first static hyperpolarizability values. The thermodynamic functions (entropy, heat capacity and enthalpy) obtained from harmonic force field calculations for the range of temperature 100–1000 K are reported. Moreover, highest occupied molecular orbital – lowest unoccupied molecular orbital (HOMO-LUMO) analysis, molecular electrostatic potential (MEP) diagram, global reactivity descriptors and condensed or atomic Fukui Functions have been also presented.

Computational and Experimental FT‐ IR, NMR, UV‐Vis Spectral Studies of 5,5′‐((4‐chlorophenyl)methylene)bis(1,3‐dimethyl‐6‐(methylamino)pyrimidine‐2,4(1H,3H)‐dione)

AbstractSynthesis of a novel 5,5′‐((4‐chlorophenyl)methylene)bis(1,3‐dimethyl‐6‐(methylamino)pyrimidine‐2,4(1H,3H)‐dione) has been done, followed by respective characterization by various spectroscopic techniques viz FT‐IR, 1H‐NMR, 13C‐NMR, UV‐Vis spectroscopy and computational methods. The study of the structure was done by Density Functional Theory (DFT) at the theory level Becke3–Lee–Yang–Parr (B3LYP) functional and 6–31G (d, p) as basis set. A close examination of various structural and thermodynamic parameters, electrostatic potential, electrophilicity (ω), chemical potential (μ), chemical hardness (η) and max amount of electronic charge transfer (▵Nmax) was done for this compound. Natural bond orbital analysis was employed to study the hyper conjugative interactions occurring within the molecule that are responsible for the stability of the molecule. To study the chemically active sites in the molecule, local reactivity descriptors were also calculated. Electric dipole moment, polarizability and first static hyperpolarizability values have been investigated for the title compound. In addition to it, a discussion about correlation graphs between 1H‐NMR and 13C‐NMR spectroscopic values is also done.

NLO properties of 1, 4-naphthoquinone, Juglone and Lawsone by DFT and Z-scan technique – A detailed study

1, 4-Naphthoquinone, 2-hydroxy-1,4-naphthoquinone (Lawsone) and 5-hydroxy-1,4-naphthoquinone (Juglone) have been investigated for their nonlinear optical (NLO) properties using Z-scan technique and Density Functional Theory (DFT) method. The Z-scan results show that all the three compounds have appreciable NLO properties. Among the three molecules Juglone showed the highest static hyperpolarizability value. The functional CAM-B3LYP performed better than BHHLYP and B3LYP in computing NLO properties. Solvent environment plays a decisive role in NLO properties of naphthoquinone derivatives. Polar solvent environment enhanced the NLO characteristics.

Computational studies of third-order nonlinear optical properties of pyridine derivative 2-aminopyridinium p-toluenesulphonate crystal

We have reported a theoretical investigation on nonlinear optical behaviour, electronic and optical properties and other molecular properties of the organic nonlinear optical crystal 2-aminopyridinium p-toluenesulphonate (APPTS). The computation has been done using density functional theory (DFT) method employing 6-31G(d) basis set and Becke’s three-parameter hybrid functional (B3LYP). Calculated values of static hyperpolarizability confirm the good nonlinear behaviour of the molecule. Electronic behaviour and global reactivity descriptor parameters are calculated and analysed using HOMO–LUMO analysis. Energy band gap and simulated UV–visible spectrum show good agreement with experimental results. Other important molecular properties like rotational constant, zero-point vibrational energy, total energy at room temperature and pressure have also been calculated in the ground state.

Solvatochromic effect on UV–vis absorption and fluorescence emission spectra, second- and third-order nonlinear optical properties of dicyanovinyl-substituted thienylpyrroles: DFT and TDDFT study

The nonlinear optical properties of dicyanovinyl-thienylpyrroles 1–6 compounds were investigated by the determining of the first-order molecular static hyperpolarizability (β) and the second-order molecular static hyperpolarizability (γ) in the ground state by using the HSEh1PBE/6-311G(d,p) level of density functional theory (DFT). The photophysical behavior of compounds 1 and 5 in polar and non-polar solvents was studied by using UV–vis absorption and fluorescence emission spectroscopies. In order to investigate the effects of these solvents, the time-dependent density functional theory (TD-DFT) calculations with the polarizable continuum model (PCM) in the excited state were performed. The UV–Vis absorption and fluorescence emission spectra for compound 5 were also simulated using TD-HSEh1PBE/6-311G(d,p) level, and the major contributions to the electronic transitions for compounds 1–6 were obtained. The β0 value (18.74×10−30esu) calculated by using HSEh1PBE/6-311G(d,p) for compound 2 is 1.49 times lower than the experimental value (28×10−30esu), and 2.34 times greater than pNA value (8×10−30esu). The β and γ parameters for compound 2 is lower than 1 and 3–6 due to electron donating pyrrole ring and electron accepting dicyanovinyl group. Moreover, we used the hybrid DFT methods (B3LYP, M062X, CAM-B3LYP and BHandHLYP) to show the accuracy for first static hyperpolarizability values for compounds 1–6. The β0 parameter for compound 5 in both polar and non-polar solvents was examined by using two level model.

Synthesis, spectral analysis and quantum chemical studies on molecular geometry of (2E,6E)-2,6-bis(2-chlorobenzylidene)cyclohexanone: Experimental and theoretical approaches

(2E,6E)-2,6-bis(2-chlorobenzylidene) cyclohexanone was synthesized and characterized by proton and carbon nuclear magnetic resonance, infrared, ultraviolet-visible, mass spectral analysis and X-ray crystallography techniques. Quantum Chemical calculations were done using Becke3-Lee-Yang-Parr with 6-31, 6-311, 6-311 + and 6-311++G (d, p) as basis sets and CAM-B3LYP with 6-31G(d,p) as the basis set. A good correlation between calculated and experimental spectroscopic data has been accomplished. Ultraviolet-Visible spectrum of the molecule was recorded in the region 200–500 nm and the electronic properties and composition were obtained using Time Dependent Density Functional Theory method. X-ray parameters (bonds, bond angles and torsion angles), Electric dipole moment, Mulliken atomic charges, polarizability and first static hyperpolarizability values have been calculated. Hyperconjugative interactions were studied with the help of natural bond orbital analysis. The thermodynamic properties of the compound were calculated at different temperatures.

Synthesis, spectral analysis (FT-IR, 1H NMR, 13C NMR and UV–visible) and quantum chemical studies on molecular geometry, NBO, NLO, chemical reactivity and thermodynamic properties of novel 2-amino-4-(4-(dimethylamino)phenyl)-5-oxo-6-phenyl-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carbonitrile

In the present study novel 2-amino-4-(4-(dimethylamino)phenyl)-5-oxo-6-phenyl-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carbonitrile was synthesized and characterized by FT-IR, 1H NMR, 13C NMR, UV–visible spectroscopy and mass spectral analysis. The chemical calculations were done by DFT level of theory using Becke3–Lee–Yang–Parr (B3LYP) and Coulomb Attenuating Method (CAM-B3LYP)/6-31G(d,p) basis set. 1H, 13C chemical shifts and vibrational wavenumbers were calculated and good correlation with the experimental data has been accomplished. UV–Visible spectrum of the molecule was recorded in the region 200–500nm and the electronic properties and composition were obtained using Time Dependent Density Functional Theory (TDDFT) method. Hyperconjugative interactions were studied with the help of natural bond orbital analysis. Electric dipole moment, polarizability and first static hyperpolarizability values have been calculated. The results show that the title compound possesses nonlinear optical behavior with non-zero values. The thermodynamic properties of the compound were calculated at different temperatures. The local reactivity descriptors show that C(7) is most reactive site for nucleophilic attack.

Fructose calcium chloride MOFs for NLO applications

Non-centrosymmetric Metal Organic Frameworks (MOF) based on coordination of carbohydrates on alkaline metal ion represent an ideal category of compounds to plan functional materials with interesting second-order non-linear optics properties. Two MOFs obtained from fructose and calcium chloride, [Ca(C6H12O6)(H2O)2]Cl2 (1) and [Ca(C6H12O6)2(H2O)2]Cl2·H2O (2), have been synthetized in ethanol and by solid-solid interactions and have been characterized with X-ray diffraction and IR and RAMAN spectroscopy. The two compounds have also been studied with DFT theoretical calculations to investigate their relative stability and foresee their optical properties. Finally, the second harmonic generation (SHG) properties have been evaluated by SHG microscopy. It has been demonstrated that the coordination of fructose on the calcium ion causes an improvement of the SHG intensity with respect to the fructose itself and that there is a strictly correlation between the calculated dipole moment and the first static hyperpolarizability values and intensity of the SHG signal. Furthermore, the remarkable difference in the SHG intensity of the two compounds studied, suggests that this physical property can be "controlled" not only by tuning the composition of the system, but also by the disposition of the MOF's building units in the crystal. The metal-carbohydrate based MOFs analyzed in this work have a favorable combination of thermal and chemical stability, transparency, and second-order optical non-linearity and are thus potential candidates for applications in electro-optic devices.

Spectroscopic (FT-IR, FT-Raman, and UV–visible) and quantum chemical studies on molecular geometry, Frontier molecular orbitals, NBO, NLO and thermodynamic properties of 1-acetylindole

Quantum chemical calculations of ground state energy, geometrical structure and vibrational wavenumbers of 1-acetylindole were carried out using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. The FT-IR and FT-Raman spectra were recorded in the condensed state. The fundamental vibrational wavenumbers were calculated and a good correlation between experimental and scaled calculated wavenumbers has been accomplished. Electric dipole moment, polarizability and first static hyperpolarizability values of 1-acetylindole have been calculated at the same level of theory and basis set. The results show that the 1-acetylindole molecule possesses nonlinear optical (NLO) behavior with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV–Visible spectrum of the molecule was recorded in the region 200–500nm and the electronic properties like HOMO and LUMO energies and composition were obtained using TD-DFT method. The calculated energies and oscillator strengths are in good correspondence with the experimental data. The thermodynamic properties of the compound under investigation were calculated at different temperatures.

Quantum-chemical (DFT, MP2) and spectroscopic studies (FT-IR and UV) of monomeric and dimeric structures of 2(3H)-Benzothiazolone

Molecular geometry and vibrational wavenumbers of 2(3H)-Benzothiazolone (C7H5NSO, HBT) was investigated using density functional (DFT/B3LYP) method with 6-311+G(d,p) basis set. The vibrational wavenumbers are found to be in good agreement with experimental FT-IR spectra. Hydrogen-bonded dimer of HBT, optimized by counterpoise correction, was studied by MP2 and DFT/B3LYP at the 6-311+G(d,p) level and the effects of molecular association through NH---O hydrogen bonding were discussed. A detailed analysis of the nature of the hydrogen bonding, using topological parameters, such as electronic charge density, Laplacian, kinetic and potential energy density evaluated at bond critical points (BCP) has also been presented. The UV absorption spectra of the compound dissolved in ethanol and chloroform solutions were recorded in the range of 200–600nm. The UV–vis spectrum of the title molecule was also calculated using TD-DFT method. The calculated energy and oscillator strength almost exactly reproduce the experimental data. Total and partial density of state (TDOS, PDOS) of the HBT in terms of HOMOs and LUMOs and molecular electrostatic potential (MEP) were calculated and analyzed. The electric dipole moment, polarizability and the first static hyper-polarizability values for HBT were calculated at the DFT/B3LYP with 6-311+G(d,p) basis set. The results also show that the HBT molecule may have nonlinear optical (NLO) comportment with non-zero values. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization was analyzed using natural bond orbital (NBO) analysis.

Structure–Property Relationships in PtII Diimine‐Dithiolate Nonlinear Optical Chromophores Based on Arylethylene‐1,2‐dithiolate and 2‐Thioxothiazoline‐4,5‐dithiolate

AbstractEighteen new [PtII(N∧N)(S∧S)] complexes [23–40; N∧N = diimine: 2,2′‐bipyridine, 1,10‐phenanthroline and alkyl/aryl‐substituted derivatives; S∧S = arylethylene‐1,2‐dithiolate (R‐edt2–: R = phenyl, 2‐naphthyl, 1‐pyrenyl), N‐substituted 2‐thioxothiazoline‐4,5‐dithiolate (R‐dmet2–: R = methyl, ethyl, phenyl)] have been synthesized and characterized by spectroscopic (UV/Vis/NIR, fluorescence) and electrochemical (CV) measurements. Single‐crystal X‐ray diffraction analysis allowed structural characterization of five of the complexes (27–29, 31, and 37). Structural modifications capable of affecting the nature and energies of the frontier molecular orbitals in these systems were assessed and hybrid DFT and time‐dependent (TD) DFT calculations, carried out both in the gas phase and in the presence of several solvents (CH2Cl2, CHCl3, CH3CN, acetone, thf, dmf, dmso, and toluene), allowed the trends observed in the voltammetric data and in the energies of the peculiar solvatochromic visible absorption bands to be rationalized. In addition, to evaluate the second‐order nonlinear optical properties of 23–40, first static hyperpolarizability values βtot were calculated both in the gas phase and in CH2Cl2, the highest values being obtained for [Pt(N∧N)(Me‐dmet)] complexes (N∧N = 4,4′‐diphenyl‐2,2′‐bipyridine and 4,7‐diphenyl‐1,10‐phenanthroline; βtot = 691 × 10–30 and 604 × 10–30 esu, respectively).

Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties: An Insight into the Electronic Properties of bis(Pyren‐1‐yl‐ethylene‐1,2‐dithiolato)Gold(III)

The electrochemical, UV/Vis-NIR absorption, and emission-spectroscopic features of (TBA(+))(1(-)) and the corresponding neutral complex 1 were investigated (TBA(+)=tetrabutylammonium; 1(-)=[Au(III)(Pyr,H-edt)(2)](-); Pyr,H-edt(2-)=pyren-1-yl-ethylene-1,2-dithiolato). The intense electrochromic NIR absorption (λ(max)=1432 nm; ε=13000 M(-1) cm(-1) in CH(2)Cl(2)) and the potential-controlled visible emission in the range 400-500 nm, the energy of which depends on the charge of the complex, were interpreted on the grounds of time-dependent DFT calculations carried out on the cis and trans isomers of 1, 1(-), and 1(2-). In addition, to evaluate the nonlinear optical properties of 1(x-) (x=0, 1), first static hyperpolarizability values β(tot) were calculated (β(tot)=78×10(-30) and 212×10(-30) esu for the cis isomer of 1(-) and 1, respectively) and compared to those of differently substituted [Au(Ar,H-edt)(2)](x-) gold dithiolenes [Ar=naphth-2-yl (2), phenyl (3); x=0, 1].

Investigations on the physicochemical properties of 2,4-dinitrophenol: Efficient organic nonlinear optical crystal for frequency doubling

Good quality single crystal of 2,4-dinitrophenol is grown by slow evaporation solution growth technique. The cell parameters are determined from the single crystal X-ray analysis. The characteristic frequencies of the various functional groups are identified by investigating FTIR and FT Raman spectra and they are assigned. The result of thermal analysis reveals the decomposition mechanism and the thermal stability of the compound. Optical transparency in the visible region, the lower cut-off wavelength and the band gap energy are estimated from the optical studies. The first order static hyperpolarizability value is calculated and it is 8.4 times greater than that of the urea. The gap between highest occupied molecular orbital and the lowest unoccupied molecular orbital is calculated, which is useful for estimating the efficiency of second harmonic generation. The crystal exhibits high relative conversion efficiency when compared to urea.

DFT studies on nonlinear optical properties of neutral nest-shaped heterothiometallic [MOS 3Py 5Cu 3X] (M = Mo, W; X = F, Cl, Br, I) clusters

Theoretical calculations were carried out on some neutral nest-shaped heterothiometallic cluster compounds [MOS 3Py 5Cu 3X] (M = Mo, W; X = F, Cl, Br, I) with the high first static hyperpolarizabilities β values. The geometries of these cluster compounds were optimized by the restricted DFT method at B3LYP level with LanL2DZ base set without any constrains. In order to understand the relationship between the first static hyperpolarizabilities and the compositions of these clusters, the frontier orbital compositions and energy gaps between the HOMO and LUMO orbitals were calculated and analysed. In these clusters the HOMO orbitals are mainly composed of halogen atoms and the first static hyperpolarizability increases from F to I atom. The LUMO orbitals of clusters [MoOS 3Py 5Cu 3X] are comprised of Mo, O and S atoms while the LUMO orbitals of clusters [WOS 3Py 5Cu 3X] composed of W atom and pyridine ring. The energy gaps between the HOMO and LUMO orbitals of the clusters [MoOS 3Py 5Cu 3X] are smaller than those of the clusters [WOS 3Py 5Cu 3X]. As a result the first static hyperpolarizability values of the clusters [MoOS 3Py 5Cu 3X] are higher than those of the clusters [WOS 3Py 5Cu 3X].

Investigations of nonlinear optical (NLO) properties of Fe, Ru and Os organometallic complexes using high accuracy density functional theory (DFT) calculations

Organometallic and coordination complexes are interesting candidates for NLO purposes. Among these materials bimetallic complexes belong to a new class of second order NLO materials. The objective of this investigation was to design a range of novel bimetallic molecular systems, which show high nonlinear optical activity. In this investigation, main attention was drawn to the ferrocenyl systems coupled with group eight metal carbonyls, where charge transfer occurs from ferrocene to the metal carbonyl moiety. These novel ferrocene bimetallic systems show high first static hyperpolarizability values. We report novel organometallic systems with high β values. The high accuracy density functional theory (DFT) was used for the investigation of NLO properties of these complexes. The full geometry optimisations of designed bimetallic systems were performed using DFT method at B3LYP/LanL2DZ level of theory using the gaussian98W. The calculations of the first static hyperpolarizabilities of these systems were performed at the same level of theory.

New advances in molecular engineering for quadratic nonlinear optics

Optimization of organic molecules for quadratic nonlinear optics is investigated in the perspective of nonlinearity/transparency trade-off, using intramolecular charge-transfer compounds with limited conjugation, such as oligomers of polysilane or polyphenyl. A large increase of the transparency in the blue and near UV spectral range is obtained for silane derivatives, but at the cost of a limitation of the nonlinear optical response at the molecular scale. On the contrary, polyphenyls appear to be ‘optimized’ materials, their nonlinear optical performances, both at the microscopic and macroscopic scale, being much better than those of paranitroanilines, with a significant improvement of the transparency. On the other hand, organometallic complexes containing ferrocene moieties conjugated to Ni, Pd or Pt metals through an organic polarizable unit display interesting nonlinear optical properties: the role of complexation appears to be quite important for ferrocenyl-containing ligands. A metal-to-metal intramolecular charge transfer is clearly evidenced. The role of the nature of the complexing metal and the influence of the nature of the ligand are also investigated. The moderate static hyperpolarizability values (of the order of 20 × 10 −30 e.s.u. may be partially accounted for by the defavourable projection factor between the ground state dipole moment and the vector part of the molecular hyperpolarizability.